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      Thermodynamic insight into stimuli-responsive behaviour of soft porous crystals

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          Abstract

          Knowledge of the thermodynamic potential in terms of the independent variables allows to characterize the macroscopic state of the system. However, in practice, it is difficult to access this potential experimentally due to irreversible transitions that occur between equilibrium states. A showcase example of sudden transitions between (meta)stable equilibrium states is observed for soft porous crystals possessing a network with long-range structural order, which can transform between various states upon external stimuli such as pressure, temperature and guest adsorption. Such phase transformations are typically characterized by large volume changes and may be followed experimentally by monitoring the volume change in terms of certain external triggers. Herein, we present a generalized thermodynamic approach to construct the underlying Helmholtz free energy as a function of the state variables that governs the observed behaviour based on microscopic simulations. This concept allows a unique identification of the conditions under which a material becomes flexible.

          Abstract

          Knowledge of the thermodynamic potential is crucial to characterize the macroscopic state of soft porous crystals. Here, the authors present a generalized thermodynamic approach to construct the Helmholtz free energy and identify the conditions under which a material becomes flexible.

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          Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set

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            Nosé–Hoover chains: The canonical ensemble via continuous dynamics

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              Flexible metal-organic frameworks.

              Advances in flexible and functional metal-organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009-2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host-guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal-organic frameworks for separation, catalysis, sensing, and biomedicine.
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                Author and article information

                Contributors
                Louis.Vanduyfhuys@UGent.be
                Veronique.VanSpeybroeck@UGent.be
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                15 January 2018
                15 January 2018
                2018
                : 9
                : 204
                Affiliations
                [1 ]ISNI 0000 0001 2069 7798, GRID grid.5342.0, Center for Molecular Modeling, , Ghent University, ; Technologiepark 903, 9052 Zwijnaarde, Belgium
                [2 ]ISNI 0000 0001 2097 0141, GRID grid.121334.6, Institut Charles Gerhardt Montpellier, , Université Montpellier, ; Place E. Bataillon, 34095, Montpellier, Cedex 05 France
                Author information
                http://orcid.org/0000-0003-4493-5708
                http://orcid.org/0000-0002-4841-2608
                http://orcid.org/0000-0003-2206-178X
                Article
                2666
                10.1038/s41467-017-02666-y
                5768703
                29335556
                c2e83450-5529-42d0-bce2-4e5b16de325f
                © The Author(s) 2018

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 21 May 2017
                : 18 December 2017
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